Catalyst-free CO₂ hydrogenation with BH₃NH₃ in water: DFT mechanistic insights

Abstract

Extensive DFT calculations show that BH3NH3 may transfer dihydrogen to CO2 rather than HCO3- in water over a barrier of 25.9 kcal/mol, followed by faster hydride transfer from borate anions...

Solvent- and catalyst-free reduction of CO2 with ammonia borane

“…24,45 Our reaction mechanism without solvent differs from previously reported CO 2 reduction with AB in water where CO 2 accepts a hydride from AB to give formate over an E a of 104.6 kJ mol −1 . 38 The main difference comes from the reactivity of DADB versus AB. The hydrolysis of AB doesn't form DADB, allowing only AB to react with CO 2 .…”

“…34,35 Previous works reported the catalytic reduction of CO 2 to formate or methanol with AB in solution. 36–38 The metal-free CO 2 conversion to formic acid with AB was also achieved with a phosphorous pincer catalyst. 39 Graphene oxide was also prepared from the reaction of CO 2 with AB without any catalyst at high pressure (4 MPa) followed by pyrolysis.…”